JP2001356526A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner exhibiting good fixing property at low temperature, offset resistance at high temperature and developing property. SOLUTION: In the toner containing a binder resin, a coloring agent, wax and an organic iron compound, the binder resin contains a hybrid resin component having 2 to 40 mgKOH/g acid value and polyester units and vinyl polymer units. The toner has a tetrahydrofuran insoluble component by 2 to 50 wt.% based on the binder resin. The tetrahydrofuran soluble component has the main peak from 2,000 to 15,000 mol.wt. by gel permeation chromatography and contains the component having >=100,000 to <10,000,000 mol.wt. by 5 to 40 wt.%, the component of >=5,000 to <100,000 mol.wt. by 40 to 70 wt.%, and the component of >=1,000 to <5,000 mol.wt. by 10 to 30 wt.%. The organic iron compound is a complex and/or complex salt of specified monoazo compounds and iron atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, or the like.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
A number of methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means, and then the electrostatic charge image is developed using a toner, and if necessary, a toner image is formed on a transfer material such as paper. Is transferred and fixed by heating, pressure, heating / pressing or solvent vapor to obtain a toner image.

Various methods and apparatuses have been developed for fixing the toner image to a sheet such as paper, which is the above-mentioned final step. Currently, the most common method is fixing using a hot roller or a heating film. This is a compression heating method using a heating heater.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasability to the toner and the toner image surface of the fixing sheet under pressure while passing the sheet. Is performed. In this method, since the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing is performed quickly Can be.

A part of the toner image adheres and transfers to the surface of the fixing roller and then re-transfers to the sheet to be fixed because the softened and melted toner image comes into contact with the surface of the heating roller under pressure. As a result, an offset phenomenon occurs, which stains the sheet to be fixed. This offset phenomenon is caused by the fixing speed,
It is greatly affected by the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

The toner on the sheet to be fixed forms several toner layers. In a system in which the fixing speed is high and the surface temperature of the heating roller is high, the temperature difference between the toner layer in contact with the heating roller and the lowermost toner layer in contact with the sheet to be fixed increases. When the surface temperature of the heating roller is high, the uppermost toner layer is excessively softened and melted, and the offset phenomenon is easily caused. When the surface temperature of the heating roller is low, the toner in the lowermost layer does not melt sufficiently to fix the toner, and a phenomenon of low-temperature offset in which the toner is not fixed on the sheet to be fixed is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing to anchor the toner to the sheet to be fixed is usually performed. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the toner can be prevented. However, since the shearing force applied to the toner becomes very large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after the separation claw for separating the sheet to be fixed from the fixing roller is separated. Easily appear in the fixed image. Further, since the pressure is high, the line image is crushed at the time of fixing, or the toner is scattered, so that the image of the fixed image is easily deteriorated.

Further, it is difficult to uniformly disperse various additives, particularly wax, added during the production of the toner, so that not only the fixing performance of the toner, but also the developability tends to be problematic. This problem is significant for certain toners.

[0009] Japanese Patent Application Laid-Open No. 62-63491,
JP-A-221967, JP-A-3-39973 and JP-A-5-72812 disclose toners containing a boron compound of benzyl acid.

Japanese Patent Application Laid-Open No. Hei 6-214421 discloses an image forming method using a toner containing an aluminum complex as a charge accelerating additive.

Japanese Patent Application Laid-Open No. 9-34174 discloses a toner in which the binder resin of the toner contains an acidic carbon black mainly containing a polyester resin and has a dielectric loss tangent of 25 or less.

Although these toners can improve the fixing property and the blocking resistance of the toner to some extent, they are insufficient to prevent the toner from offsetting to a heating roller or a heat-resistant film as a heating member of a fixing device.

[0013]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems.

That is, the object of the present invention is good even for a medium-to-high-speed machine using a hot roll fixing device, or a medium-to-low-speed machine using a press-bonding heat fixing method using a fixed heating heater via a heat-resistant film. An object of the present invention is to provide a toner which exhibits excellent low-temperature fixability and excellent high-temperature offset resistance.

It is an object of the present invention to provide a low-temperature fixability which exhibits good halftone fixability even when used as a binder resin for a toner having a reduced particle diameter and an increased content of a colorant (particularly a magnetic substance). It is to provide an excellent toner.

[0016]

According to the present invention, there is provided a toner containing a binder resin, a colorant, a wax and an organic iron compound, wherein (a) the binder resin of the toner has an acid value of 2 to 40 mg.
KOH / g, (b) the binder resin of the toner contains a hybrid resin component having a polyester unit and a vinyl polymer unit, and (c) the binder resin of the toner is based on the binder resin. (D) a tetrahydrofuran (THF) -soluble component of the binder resin of the toner having a molecular weight of 2 to 50% by mass in a chromatogram measured by gel permeation chromatography (GPC). 2000 to 1
It has a main peak at 15,000, contains 5 to 40% by mass of a component having a molecular weight of 100,000 to less than 10,000,000, and contains 40 to 70% of a component having a molecular weight of 5000 to less than 100,000.
(E) an organic iron compound comprising a monoazo compound represented by the following formulas (I) to (III) and a complex comprising an iron atom: And / or a complex salt.

[0017]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R
₈ is each independently hydrogen, halogen, nitro,
A linear or branched alkyl or haloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group,
It represents a substituent selected from the group consisting of a substituted or unsubstituted aralkyl group. )

[0018]

Embedded image (Wherein, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ ,
R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ each independently represent hydrogen, a halogen, a nitro group, a linear or branched alkyl or haloalkyl group having 1 to 20 carbon atoms,
It represents a substituent selected from the group consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted aralkyl group. )

[0019]

According to the study of the present inventors, in order to prevent the fixing member from being contaminated by offset regardless of the heating method of the fixing device, the low-temperature fixing property and the high-temperature offset resistance of the toner are improved. Alone is not sufficient, and it has been found that it is important to improve the releasability of the toner from the fixing member.

Conventionally, improvement of the toner offset phenomenon and improvement of the fixability of the toner have been regarded as the same. However, this is accompanied by the improvement of the fixability by the improvement of the binder resin and the wax contained in the toner. Improving the offset in such a way is limited and inadequate.

In the case where the releasability of the toner is insufficient even if the releasability of the fixing member and the cleaning member is improved,
Even if a sufficient offset preventing effect can be expected in the initial stage of use of these members, if they are used for a long period of time, the members will deteriorate over time, and eventually offset may occur.

Conventionally, the binder resin of the toner is chloroform,
The inclusion of an insoluble component in an organic solvent such as THF is proposed from the viewpoint of improving the hot offset resistance of the toner. However, even with such a toner, aged fixing members,
In some cases, a sufficient offset prevention effect is not exerted on the cleaning member. Further, the toner may contain wax for the purpose of imparting releasability, but it is necessary to contain a large amount of wax in order to maintain a sufficient offset prevention effect on the aged fixing member and cleaning member. There is. In this case, problems such as a decrease in image developability due to durability, an increase in fog density due to durability, and the like may occur. Further, it is difficult to control the dispersion state of the wax contained in the toner particles, and the toner contains a large amount of the released wax.
As a result, the toner on the photoconductor may not be sufficiently cleaned and may remain, resulting in an image defect.

In the toner of the present invention, in order to maintain a sufficient offset prevention effect even with respect to the aged fixing member and the cleaning member, it is necessary to achieve both improvement of the toner releasability and development of the toner. .

According to the study of the present inventor, the toner has a specific acid value, the binder resin is a hybrid resin having a polyester unit and a vinyl polymer unit, and contains a specific THF-insoluble component. THF of toner binder resin
This is achieved by a toner in which the soluble component has a main peak in a specific molecular region, contains a specific molecular weight component, and has a specific dielectric loss tangent (tan δ).

In the toner of the present invention, the binder resin may have an acid value of 2 to 40 mgKOH / g, preferably 5 to 30 mgKOH / g, and more preferably 7 to 25 mgKOH / g. It is. If the acid value of the binder resin is less than 2 mgKOH / g or more than 40 mgKOH / g, the monoazo compound represented by the above formulas (I) to (II) and the iron atom are used as charge control agents. In the toner containing the organic iron compound comprising, the dispersion of the organic iron compound is not always in a suitable state, and the image density may decrease due to durability, which is not preferable.

In the toner of the present invention, the binder resin contained in the toner contains a hybrid resin component having a polyester unit and a vinyl polymer unit. The presence of the hybrid resin component can be confirmed by ¹³ C-NMR measurement. ^In the case of a magnetic toner containing a magnetic substance that impairs the resolution of the ¹³ C-NMR spectrum, the magnetic toner is added to a concentrated aqueous hydrochloric acid solution and stirred at room temperature for 70 to 80 hours to dissolve the magnetic substance. It can be measured as a measurement sample. Further, a toner containing carbon black and an organic pigment can be used as a measurement sample as it is. ¹³ C-NM when acrylic ester is used as a vinyl polymer below
An example of the measurement result of R is shown.

[0027]

[Table 1]

In the toner of the present invention, the binder resin contained in the toner contains 2 to 50% by mass of a THF-insoluble component, preferably 5 to 40% by mass, and more preferably. Contains from 7 to 30% by mass. If the T contained in the binder resin of the toner
Regardless of whether the HF-insoluble content is less than 2% by mass or more than 50% by mass, the toner containing the organic iron compound as a charge control agent disperses the wax contained in the toner. It is difficult to maintain an optimal state, and toner adhesion to the fixing member may become apparent due to durability, which is not preferable.

The toner of the present invention has a molecular weight of 2,000
To have a main peak in a region having a molecular weight of 3,000 to 10,000, preferably having a main peak in a region having a molecular weight of 3,000 to 10,000, and more preferably having a main peak in a region having a molecular weight of 4,000 to 9000. It is. If there is no main peak in the molecular weight region, the toner may not be able to satisfy the hot offset resistance and the blocking resistance, which is not preferable.

In the toner of the present invention, the THF-soluble component of the binder resin contained in the toner contains 5 to 40% by mass of a component having a molecular weight of 100,000 to less than 10,000,000, and preferably 7 to 40% by mass. The content is 35% by mass, more preferably 10 to 30% by mass. If the molecular weight component is less than 5% by mass, the high-temperature offset resistance of the toner may be deteriorated, and if it is more than 40% by mass, the low-temperature fixability of the toner may be deteriorated. Absent.

The THF-soluble component of the binder resin contained in the toner is 40 components of a molecular weight of 5,000 or more and less than 100,000.
To 70% by mass, preferably 42% by mass.
To 68% by mass, more preferably 4% by mass.
This is the case when the content is 5 to 65% by mass. If the molecular weight component is contained in less than 40% by mass or more than 70% by mass, the dispersion of the organic iron compound contained as a charge control agent in the toner can be kept in a suitable state. It is difficult, and the image density may decrease due to durability, which is not preferable.

The THF-soluble component of the binder resin contained in the toner may be a component having a molecular weight of 1,000 or more and less than 5,000.
It is contained in an amount of 0 to 30% by mass, preferably 1 to 30% by mass.
The content is 2 to 28% by mass, and more preferably the content is 15 to 25% by mass. If the molecular weight component is less than 10% by mass, the low-temperature fixability of the toner may be deteriorated, and if it is more than 30% by mass, the blocking resistance of the toner may be deteriorated. Not preferred.

In the toner of the present invention, a frequency of 100 k
The dielectric loss tangent (tan δ) of the toner measured in Hz is 3 × 1
0^-3~ 3 × 10^-2, But preferably 4 × 1
0^-3~ 2 × 10^-2And more preferably
5 × 10^-3~ 1.5 × 10 ^-2This is the case. Also
And the dielectric loss tangent of the toner is 3 × 10^-3If less than
Is a problem with the stability of toner image density under normal temperature and low humidity environment
And a dielectric loss tangent of 3 × 10^-2A place to be super
In a high-temperature, high-humidity environment,
May cause problems with toner image density stability.
Not preferred.

In the toner of the present invention, the monoazo compound represented by the above formulas (I) to (II) and the organic iron compound comprising an iron atom are used as a charge controlling agent in the toner in an amount of 0.1 to 5%.
%, Preferably 0.5 to 3% by mass.
%, More preferably 0.7 to 2% by mass. If the amount of iron element contained in the toner is less than 0.1% by mass or more than 5% by mass, the effect of the present invention cannot be sufficiently exhibited.

According to the study of the present inventor, it is not enough to simply improve the low-temperature fixing property and the high-temperature offset resistance of the toner in order to prevent the fixing member from being contaminated by offset regardless of the heating method of the fixing device. It was found that it was important to improve the releasability of the toner from the fixing member.

Conventionally, improvement of the toner offset phenomenon and improvement of the fixability of the toner have been regarded as the same, but this is accompanied by the improvement of the fixability by improving the binder resin and the wax contained in the toner. Improving the offset in such a way is limited and inadequate.

In the case where the releasability of the fixing member and the cleaning member, which are determined by the contact angle of water or toner, is not sufficient, if the releasability of the toner is insufficient, sufficient offset prevention is required at the initial stage of use. Even if the effect can be expected, if used for a long period of time, each member may deteriorate over time, and eventually an offset may occur.

Conventionally, it has been proposed that the binder resin of the toner has an insoluble component in an organic solvent such as THF from the viewpoint of improving the hot offset resistance of the toner. However, even such a toner has deteriorated over time. In some cases, a sufficient offset prevention effect is not exerted on the fixing member and the cleaning member. Further, the toner may contain wax for the purpose of imparting releasability. However, a large amount of wax is contained in the aged fixing member and the cleaning member in order to maintain a sufficient offset prevention effect. There is a need. In this case, problems such as the toner developability, that is, a decrease in image density and an increase in fog density occur, and it is difficult to control the dispersion state of the wax contained in the toner particles. A large amount of wax. As a result, the toner on the photoconductor may not be sufficiently cleaned and may remain, resulting in an image defect.

The wax contained in the toner of the present invention is:
The Mp measured by GPC may be 400 to 20,000 and the ratio (Mw / Mn) may be 1.2 to 20, but is preferably 700 to 15000, and the ratio (Mw / Mn) is 1.
5 to 15, more preferably 900 to 10000, and the ratio (Mw / Mn) is 1.7 to 10. If Mp is less than 400, the ratio (Mw / M
When n) is less than 1.2, the dispersed particle size of the wax in the toner particles is too small, and Mp is 20,000.
If the ratio (Mw / Mn) is more than 20, the dispersed particle size becomes too large, and in either case, it is difficult to control the dispersed particle size of the wax, which is not preferable.

The toner of the present invention may contain two or more different waxes, in which case the GPC
Mp measured at 300 to 20000, ratio (Mw /
Mn) may be 1.5 to 25, but preferably 4
00 to 15000, ratio (Mw / Mn) 1.8 to 2
2, more preferably 500 to 100
00, where the ratio (Mw / Mn) is 2 to 20. If Mp is less than 300, ratio (Mw / Mn) is 1.
When it is less than 5, Mp is over 20,000 and the ratio (Mw / M
In both cases where n) is more than 25, the particle size distribution of the wax in the toner particles is widened and it is difficult to control, which is not preferable.

The wax contained in the toner of the present invention is:
They are selected from hydrocarbon waxes, polyethylene waxes and polypropylene waxes.

The wax contained in the toner of the present invention is:
A wax such as a synthetic hydrocarbon obtained from the distillation residue of a hydrocarbon obtained by the Age method consisting of carbon monoxide and hydrogen or by hydrogenating them is preferred. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are more preferably used.

The wax contained in the toner of the present invention comprises:
It has a structure represented by the formula (1).

[0044]

Embedded image In the formula, A represents a hydroxyl group or a carboxyl group;
It represents an integer of 0 to 60, preferably A represents a hydroxyl group, and a represents an integer of 30 to 50.

The wax contained in the toner of the present invention is:
In the case of acid-modified polyethylene, 1 to 20 mgK
It has an acid value of OH / g and is obtained by modifying polyethylene with an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride, preferably from 1.5 to 15mgK
It has an acid value of OH / g.

The wax contained in the toner of the present invention is
1-20 mg when acid-modified polypropylene
Having an acid value of KOH / g and polyethylene as maleic acid,
It is modified with an acid monomer selected from at least one of maleic acid half ester and maleic anhydride, preferably 1.5 to 15 mg
It has KOH / g.

When two kinds of wax are contained in the toner of the present invention, it is preferable that at least one kind of wax uses the above-mentioned wax.

Preferred combinations of waxes when the toner of the present invention contains two types of waxes are shown in Table 2 below.

[0049]

[Table 2]

The wax contained in the toner of the present invention comprises:
Differential scanning calorimeter (DSC) for toner containing wax
In the DSC curve measured at
° C, preferably has an endothermic main peak in the temperature range of 75 to 140 ° C, more preferably 80 to 13 ° C.
It has an endothermic main peak in the region of 0 ° C. and has an endothermic sub-peak or endothermic shoulder at the same time. If there is an endothermic main peak outside the above temperature range, it is difficult to satisfy all of the low-temperature fixing property, hot offset resistance and blocking resistance.

In the toner of the present invention, the wax is added to and dispersed in the toner in the kneading step. Preferably, the wax is added in the step of producing polyester as a binder resin. In this case, uniform dispersion of the wax is further facilitated.

When the toner of the present invention contains two or more different waxes, the wax added when the vinyl polymer is dissolved in a solvent such as xylene is preferably a hydrocarbon wax or polyethylene. Polymer, polypropylene polymer, 1 to 20 mg KOH /
g of acid-modified polypropylene having an acid value of 1 to 20 g
It is an acid-modified polyethylene having an acid value of mgKOH / g.

The following are specific examples of the monoazo compound preferably used in the present invention, but the present invention is not limited to these monoazo compounds.

[0054]

Embedded image

The monoazo iron compound used in the toner of the present invention is a monoazo iron compound represented by the following formulas (A), (B) and (C) or a mixture thereof.

[0056]

Embedded image (Where A and B each represent a benzene ring residue and / or a naphthalene ring residue; at least one of A and B represents an alkyl group; C represents a cation; and hydrogen, sodium, potassium, etc. Represents an alkali metal, ammonium, or organic ammonium.)

In the toner of the present invention, the hybrid resin composition having a vinyl polymer unit and a polyester unit contained in the binder resin is a vinyl resin obtained by addition polymerization of an aromatic vinyl monomer and a (meth) acrylate monomer. A polymer unit and a polyester unit are chemically bonded. The polyester unit contains an alcohol component and / or a carboxylic acid having an effect of controlling the dispersion of the wax.

The hybrid resin composition is formed by a transesterification reaction between an alcohol which is a polyester monomer and a (meth) acrylate. In the above hybrid resin composition, it is sufficient that 10 to 60 mol% of the (meth) acrylic acid ester constituting the vinyl polymer unit has undergone an esterification reaction with the polyester unit, but preferably 15 to 50 mol%. Reaction, more preferably 20 to 45 mol% esterification. If one of the (meth) acrylates constituting the vinyl polymer unit
When the esterification reaction with the polyester unit is less than 0 mol%, it is difficult to control the dispersion state of the wax, and when it exceeds 60 mol%, components having a relatively large molecular weight increase. As a result, the low-temperature fixability of the toner may decrease, which is not preferable.

The composition of the polyester unit and the vinyl polymer unit constituting the hybrid resin composition may be from 30:70 to 90:10 by mass ratio, but is preferably from 40:60 to 80:20. And more preferably 50:50 to 70:30. If the composition ratio of the polyester unit forming the hybrid resin composition is less than 30% by mass or more than 90% by mass, the interaction between the hybrid resin composition and the organoaluminum compound is optimized. And it is difficult to control the dispersion state of the wax, which is not preferable.

In the toner of the present invention, examples of the polyester monomer include the following.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the following formula (2) and a compound represented by the following formula (3) The diols shown are mentioned.

[0062]

Embedded image (In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

[0063]

Embedded image

As the acidic component, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof;
Succinic acid or an anhydride thereof substituted with an alkyl group having 6 to 12 carbon atoms; and unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

The following are examples of the vinyl-based monomer for producing the vinyl-based resin.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinyldene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylates such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

In the toner of the present invention, the polyester unit of the binder resin has a cross-linked structure cross-linked with a trivalent or higher polyhydric carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol. Things. Examples of the trivalent or higher polycarboxylic acid or its anhydride include, for example, 1,
2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and acid anhydrides or lower alkyl esters thereof, and the like. Examples of the polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol and the like. Preferably, 1,2,4-benzenetricarboxylic acid and its acid anhydride are used. is there.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a cross-linked structure cross-linked by a cross-linking agent having two or more vinyl groups. Examples of the agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; and diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate and 1,1.
3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; for example, polyacrylates such as polyacrylates linked by a chain containing an aromatic group and an ether bond Oxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; polyester-type diacrylates include, for example, MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These cross-linking agents may be used in combination with other monomer components 10
0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) can be used with respect to 0 parts by mass.

Among these crosslinkable monomers, those which are preferably used in terms of fixability and anti-offset property to the toner resin include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and one ether bond. And diacrylate compounds linked by a chain.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid or anhydrides thereof are exemplified. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins is used. Alternatively, a method obtained by polymerizing both resins is preferable.

The polymerization initiator used for producing the vinyl copolymer of the present invention includes, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-
Bis (t-butylperoxy) butane, t-butylhydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
Di-t-butyl peroxyazelate.

In the toner of the present invention, the vinyl polymer contained in the binder resin is preferably a vinyl monomer having a carboxyl group, and is preferably acrylic acid or methacrylic acid. 1
To 1 part by mass.

Examples of the production method for preparing the binder resin used in the toner of the present invention include the following (1) to (1).
The manufacturing method shown in (6) can be mentioned.

(1) A method in which a vinyl resin, a polyester resin and a hybrid resin component are blended after production, respectively. The blend dissolves and swells in an organic solvent (for example, xylene) and then distills off the organic solvent. It is preferably produced by adding a wax in this blending step. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. Can be used.

(2) After the production of the vinyl polymer unit,
This is a method for producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(3) This is a method for producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl monomer and / or a vinyl polymer unit. Preferably, a wax is added in this step.

(4) After the production of the vinyl polymer unit and the polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. You. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(5) After the production of the hybrid resin component, a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to thereby form a vinyl polymer unit and a polyester. The unit is manufactured. In this case, as the hybrid resin component, one produced by the production method of the above (2) to (4) can be used, and if necessary, one produced by a known production method can be used. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(6) A vinyl-based polymer unit, a polyester unit and a hybrid resin component are produced by mixing a vinyl-based monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction. Is done. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

In the production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used as the vinyl polymer unit and / or polyester unit.

Among the above-mentioned production methods (1) to (6), the production method (3) is particularly easy to control the molecular weight of the vinyl polymer unit and can control the production of the hybrid resin component. When a wax is added, the dispersion state is preferably controlled.

As the magnetic substance used in the present invention, magnetic iron oxides containing different elements, such as magnetite, maghemite, and ferrite, and mixtures thereof are preferably used.

Among them, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, sulfur,
Germanium, titanium, zirconium, tin, lead, zinc,
Calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium,
Magnetic iron oxide containing at least one element selected from indium, silver, palladium, gold, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium and bismuth is preferable. Especially lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium,
Tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper,
Zinc and gallium are preferred. Most preferably, it is a magnetic iron oxide containing an element selected from the group consisting of magnesium, aluminum, silicon, phosphorus and zirconium as a different element. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may exist as oxides or hydroxides on the surface. It is a preferred embodiment that it is contained as an oxide.

These elements can be incorporated into particles by adjusting the pH by mixing salts of the respective elements during the formation of the magnetic material. In addition, precipitation can be performed on the particle surface by adjusting the pH after the formation of the magnetic particles or adjusting the pH by adding a salt of each element.

The magnetic material containing these elements is well compatible with the binder resin and has very good dispersibility. Furthermore, this good dispersibility can improve the dispersibility of the organic iron compound used in the present invention, and the effect of the organic iron compound of the present invention can be sufficiently exhibited. The magnetic material acts as a dispersion medium, and the dispersion of the organic iron compound is assisted by the good dispersibility of the magnetic material, and the dispersibility of the organic iron compound is improved. In addition, these magnetic substances have an effect of adsorbing water molecules and facilitating the organic iron compound to easily emphasize charging by water molecules. This effect can be exhibited more effectively when used together with a binder resin having an acid value.

These magnetic materials have a uniform particle size distribution.
In combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. Further, in recent years, the toner particle diameter has been reduced, and the weight average particle diameter is 2.5 to 10%.
Even in the case of μm, the uniformity of charging is promoted, the cohesion of the toner is reduced, and the developability such as improvement of image density and improvement of fog is improved. In particular, the weight average particle size is 2.5 to 6.0.
With a μm toner, the effect is remarkable, and an extremely high-definition image can be obtained. It is preferable that the weight average particle size is 2.5 μm or more, since sufficient image density can be obtained. On the other hand, as the particle size of the toner progresses, the release of the iron compound also easily occurs.However, the toner of the present invention is excellent in charge uniformity, so that the toner is less susceptible to sleeve contamination even if some iron compound is present. Become. The magnetic toner preferably has a weight average particle size of 2.5 to 10 μm (more preferably, 2.5 to 6.0 μm). Even in the case of a non-magnetic toner, the weight average particle size is preferably from 2.5 to 10 μm, more preferably from 2.5 to 6.0 μm.

As channels, 2.00 to 2.52
less than 2.5 μm; less than 2.52 to 3.17 μm;
4. less than 4.00 μm; 4.00 to less than 5.04 μm;
04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to 1
2.70 μm or less; 12.70 to less than 16.00 μm;
16.00 to less than 20.20 μm; 20.20 to 25.
Less than 40 μm; 25.40 to less than 32.00 μm; 3
13 channels of 2.00 to less than 40.30 μm are used.

The content of these different elements is preferably 0.05 to 10% by mass based on the iron element of the magnetic iron oxide. More preferably 0.1 to 7% by mass,
Particularly preferably, it is 0.2 to 5% by mass, more preferably 0.3 to 4% by mass. If the content is less than 0.05% by mass, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. If the content is more than 10% by mass, the amount of charge release is increased, resulting in insufficient charging, which may result in lower image density or increased fog.

[0094] In the content distribution of these different elements, it is preferable that the one which is present more in the vicinity of the surface of the magnetic material. For example, when the dissolution rate of the iron element in the iron oxide is 20%, the dissolution rate of the different element is 20% of the total amount of the different element.
% To 100% is preferred. Further, it is preferably from 25% to 100%, particularly preferably from 30% to 100%. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved.

These magnetic materials have a number average particle size of 0.05.
To 1.0 μm, more preferably 0.1 to 0.5 μm
Are preferred. The magnetic material has a BET specific surface area of 2 to 40.
m ² / g (more preferably, 4~20m ² / g) it is preferably used for. The shape is not particularly limited, and an arbitrary shape is used. As magnetic properties, the magnetic field 79
Saturation magnetization is 10 to 200 Am ² / k under 5.8 kA / m
g (more preferably, 70 to 100 Am ² / kg), and the residual magnetization is 1 to 100 Am ² / kg (more preferably, 2 to 100 Am ² / kg).
To ²⁰ Am2 / kg) and those having a coercive force of 1 to 30 kA / m (more preferably, 2 to 15 kA / m) are preferably used. These magnetic materials are used in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

The amount of elements in the magnetic iron oxide is measured by X-ray fluorescence analysis using a fluorescent X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) in accordance with JIS K0119 general rules for X-ray fluorescence analysis. can do. Regarding element distribution, the amount of elements dissolved in hydrochloric acid or hydrofluoric acid is measured and quantified by plasma emission spectroscopy (ICP), and the dissolution rate is determined from the concentration of each element in each dissolution with respect to the concentration of each element in total dissolution. Is obtained by

The number average diameter can be determined by measuring a photograph enlarged and taken with a transmission electron microscope with a digitizer or the like. The magnetic properties of the magnetic material are values measured using an “oscillating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 795.8 kA / m. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The colorant that can be used in the toner of the present invention includes any suitable pigment or dye. For example, as pigments, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 100 parts by mass of the binder resin.
An addition amount of 20 parts by mass, preferably 0.2 to 10 parts by mass is good. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, per 100 parts by mass of the binder resin is good. .

In the present invention, it is preferable that an inorganic oxide such as silica, alumina, or titanium oxide, or an inorganic fine powder having a small particle diameter such as carbon black or carbon fluoride is externally added to the toner particles.

The fine silica powder, fine alumina powder or fine titanium oxide powder is preferably formed into fine particles when dispersed on the surface of the toner particles, since the fluidity-imparting property becomes higher.
The number average particle size is preferably from 5 to 100 nm, more preferably from 5 to 50 nm. Preferably as maternal fine powder in the range of 30 m ² / g or more in specific surface area according to the measured nitrogen adsorption (especially 60~400m ² / g) by the BET method, the surface-treated fine powder, 2
0 m ² / g or more (especially 40 to 300 m ² / g) in the range are preferred.

The application amount of these fine powders is
An appropriate surface coverage is obtained when 0.03 to 5 parts by mass is added to 00 parts by mass.

The hydrophobicity of the inorganic fine powder used in the present invention is preferably 30% or more, more preferably 50% or more, in terms of methanol wettability. As the hydrophobizing agent, a silane compound which is a silicon-containing surface treating agent and silicone oil are preferable.

For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane and butyltrimethoxysilane; dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethyl Silane coupling agents such as chlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane can be used.

The toner of the present invention may be mixed with a carrier and used as a two-component developer. The resistance value of the carrier is preferably adjusted to 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

Examples of the resin for coating the carrier surface include a styrene-acrylate copolymer, a styrene-methacrylate copolymer, an acrylate copolymer, a methacrylate copolymer, a silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium.

As the additives for imparting various properties used in the present invention, for example, the following are used.

(1) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.) and carbides (silicon carbide, etc.), metal salts (sulfuric acid, etc.) Calcium, barium sulfate, calcium carbonate).

(2) Lubricants: fluororesin powder (polyvinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.) and the like.

(3) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, resin fine particles and the like.

These additives are used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner particles. These additives are
They may be used alone or in combination.

In the case of a magnetic toner, it is preferable to use fine powders of two or more kinds of inorganic oxides or metal oxides in order to obtain the durability stability of development and the development stability after standing. In the case of a non-magnetic one-component developing method, it is preferable to use titanium oxide or alumina in order to improve fluidity and obtain image uniformity.

As a method for producing the toner of the present invention,
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is kneaded well using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if desired, the desired additive and toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention.

Next, an image forming method in which the toner of the present invention is preferably used will be described.

First, the developing means applicable to the image forming method of the present invention will be described.

In FIG. 1, an image carrier for carrying an electrostatic charge image formed by a known process, for example, an electrophotographic photosensitive drum 7 is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrying member carries the toner 10 as a one-component developer supplied from the hopper 9 and
By rotating in the manner, the toner 10 is transported to the developing section D where the developing sleeve 14 and the photosensitive drum 7 are opposed.
When the toner 10 is a magnetic toner, a magnet 11 is disposed in the developing sleeve 14 in order to magnetically attract and hold the toner 10 on the developing sleeve 14. Toner 10
Obtains a triboelectric charge capable of developing an electrostatic image on the photosensitive drum 7 by friction with the developing sleeve 14.

In order to regulate the layer thickness of the toner 10 conveyed to the developing section D, when the toner is a magnetic toner, the regulating magnetic blade 8 made of a ferromagnetic metal has a thickness of about 200 to 300 μm from the surface of the developing sleeve 14. It is suspended from the hopper 9 so as to face the developing sleeve 14 with a gap width. When the magnetic lines of force from the magnetic pole N1 of the magnet 11 concentrate on the blade 8, the toner 10
Is formed. As the blade 8, a non-magnetic blade can be used. When the toner 10 is a non-magnetic toner, an elastic blade such as urethane rubber, silicone rubber, or a chip blade is used.

Toner 1 formed on developing sleeve 14
0 is the thickness of the developing sleeve 14 in the developing section D.
It is preferable that the distance be smaller than the minimum gap between the photosensitive drum 7 and the photosensitive drum 7. The developing method of the present invention is particularly effective for a developing device of a system that develops an electrostatic image with such a thin toner layer (that is, a non-contact developing device). But,
The developing method of the present invention can also be applied to a developing device (that is, a contact type developing device) in which the thickness of the toner layer in the developing section is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7. .

Hereinafter, an example of the non-contact type developing device will be described.

A developing bias voltage is applied to the developing sleeve 14 by a power supply 15 in order to fly the toner 10 which is a one-component developer carried on the developing sleeve 14. When using a DC voltage as the developing bias voltage,
It is preferable that a voltage having a value between the potential of the image portion of the electrostatic charge image (the region where the toner 10 adheres and is visualized) and the potential of the background portion is applied to the developing sleeve 14. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 14 to form an oscillating electric field in which the direction is alternately reversed in the developing unit D. In this case, it is preferable to apply to the developing sleeve 14 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.

In so-called regular development in which toner is adhered to a high potential portion of an electrostatic charge image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic charge image is used. On the other hand, in the reversal development in which toner is attached to a low potential portion of an electrostatic image to visualize the toner, toner charged to the same polarity as the polarity of the electrostatic image is used. The high potential and the low potential are expressed by absolute values. In any case, the toner 10 is charged to a polarity for developing an electrostatic image by friction with the developing sleeve 14.

In the developing device of FIG. 2, as a member for regulating the layer thickness of the toner 10 on the developing sleeve 14, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel is used. An elastic plate 17 made of a material having the following characteristics is used, and this elastic plate 17 is pressed against the developing sleeve 14. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8. Other configurations of the developing device of FIG. 2 are basically the same as those of the developing device shown in FIG. 1, and the same reference numerals in FIG. 2 as those shown in FIG. 1 indicate the same members.

In the developing device shown in FIG. 2 in which the toner layer is formed on the developing sleeve 14 as described above, the toner is rubbed on the developing sleeve 14 by the elastic plate 17, so that the amount of triboelectric charge of the toner is large. Thus, the image density is improved. Such a developing device is used for a non-magnetic one-component toner.

The sleeve as the developer carrier used in the present invention preferably has a cylindrical substrate and a coating layer (resin layer) covering the surface of the substrate. Its configuration is as shown in FIG. The resin layer 1 includes a binder resin 4,
In some cases, conductive material 2, filler 3, solid lubricant 5
And is coated on the cylindrical substrate 6. When the conductive material 2 is contained, the resin layer 1 is conductive, so that excessive charging of the toner can be prevented. When the filler 3 is contained, abrasion of the resin layer 1 by the toner is prevented, and further, charging of the toner can be suitably controlled by the charge imparting property of the filler 3. When the solid lubricant 5 is contained, the releasability of the toner from the sleeve is improved, and as a result, the fusion of the toner onto the sleeve can be prevented.

In the sleeve of the present invention, when the resin layer contains a conductive substance, the volume resistance of the resin layer is 10 ⁶
Ω · cm or less, preferably 10 ³ Ω · cm or less is good. When the volume resistance of the resin layer exceeds 10 ⁶ Ω · cm, toner charge-up is likely to occur, which may cause the occurrence of blotches and the deterioration of development characteristics.

The surface roughness of the resin layer is preferably in the range of 0.2 to 3.5 μm in JIS center line average roughness (Ra). If Ra is less than 0.2 μm, the charge amount of the toner in the vicinity of the sleeve becomes too high, the toner is attracted to the sleeve by the mirroring power, new toner cannot be charged by the sleeve, and the developing property is reduced. Ra
Exceeds 3.5 μm, the toner coating amount on the sleeve is excessively increased, so that the toner cannot obtain a sufficient charge amount, and becomes non-uniformly charged, which causes a reduction in image density and uneven density.

Next, each material constituting the resin layer 1 will be described.

In FIG. 3, examples of the conductive substance 2 include metal powders such as aluminum, copper, nickel and silver; metal oxides such as antimony oxide, indium oxide and tin oxide; carbon fibers, carbon black and graphite. And carbon allotropes. Among them, carbon black is particularly excellent in electric conductivity, and is preferably used because it can be filled with a polymer material to impart conductivity, or by controlling the amount of addition, a certain degree of conductivity can be obtained. The number average particle diameter of the carbon black used in the present invention is 0.001 to 1.0 μm, preferably 0.01 to 1.0 μm.
It is preferably from μm to 0.8 μm. If the number average particle size of the carbon black exceeds 1 μm, it becomes difficult to control the volume resistance of the resin layer, which is not preferable.

The amount of the conductive substance used is as follows.
The amount is preferably from 0.1 to 300 parts by mass, more preferably from 1 to 100 parts by mass, per 100 parts by mass.

As the filler 3, a conventionally known negative charge control agent for toner or a positive charge control agent for toner may be added. Other substances include inorganic compounds such as alumina, asbestos, glass fiber, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, silica, calcium silicate; phenolic resins, epoxy resins, melamine resins, silicone resins, P
MMA, terpolymer of methacrylate (for example, polystyrene / n-butyl methacrylate / silane terpolymer), styrene-butadiene copolymer, polycaprolactone; nitrogen-containing compounds such as polycaprolactam, polyvinylpyridine, polyamide; polyvinylidene fluoride;
Polyvinyl chloride, polytetrafluoroethylene, polytetrachlorofluoroethylene, perfluoroalkoxylated ethylene, polytetrafluoroalkoxyethylene, fluorinated ethylene propylene-polytetrafluoroethylene copolymer, trifluorochloroethylene-vinyl chloride copolymer, etc. Highly halogenated polymers; polycarbonates, polyesters. Among them, silica and alumina are preferably used because they have their own hardness and charge controllability to the toner.

The amount of filler used is 100
It is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to parts by mass.

Examples of the solid lubricant 5 include molybdenum disulfide, boron nitride, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, and talc. Among these, graphite is preferably used because it has conductivity together with lubricity, and has a function of reducing toner having an excessively high charge and providing a charge amount suitable for development.

The amount of the solid lubricant used is as follows.
The amount is preferably from 0.1 to 300 parts by mass, more preferably from 1 to 150 parts by mass, per 100 parts by mass.

In some cases, as the binder resin 4 in which the conductive substance 2, the filler 3, and the solid lubricant 5 are dispersed,
Resins such as phenolic resins, epoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyolefin resins, silicone resins, fluorine resins, styrene resins, and acrylic resins are used. Particularly, a thermosetting or photocurable resin is preferable.

In the present invention, in order to suitably expose the conductive material, filler or solid lubricant in the resin layer on the sleeve surface to the surface, or to smooth the surface to form a uniform uneven surface. For this reason, it is possible to impart more preferable performance by smoothing the surface by means such as polishing described below. In particular, it is effective for the vertical streak phenomenon that occurs in solid black and halftone images and the rise of the initial image density, and is particularly effective under high temperature and high humidity. Polishing with a belt-like abrasive material to which felt or abrasive grains are adhered makes it possible to finish the surface unevenness of the sleeve evenly, so that the amount of toner coating on the sleeve is uniform and as a result, triboelectric charging with the sleeve is reduced. Only the received toner is transported to the development area. Therefore, it is considered that the above effects can be obtained.

Even after the smoothing treatment as described above, the surface of the coat layer has a Ra of 0.1 in JIS B 0601.
It is preferable to maintain irregularities in the range of 2 to 3.5 μm, more preferably about 0.3 to 2.5 μm.
The reason is the same as above.

As the cylindrical substrate 6, a non-magnetic metal cylindrical tube,
A resin cylinder is preferably used, and for example, a nonmagnetic cylindrical pipe such as a stainless steel cylindrical pipe, an aluminum cylindrical pipe, and a copper alloy cylindrical pipe is used. As a method of manufacturing a cylindrical tube, there are a drawing method and an extrusion method. In order to further increase the dimensional accuracy of the cylindrical tube itself, cutting or polishing is performed to obtain a predetermined dimensional accuracy. The straightness of the cylindrical tube is preferably 30 μm or less, more preferably 20 μm or less, and a good image is obtained. If necessary, a roughened surface may be formed by sandblasting or polishing in order to impart appropriate unevenness to the surface. Abrasive grains used for blasting may be regular particles or irregular particles.

Next, an image forming method to which the developing method of the present invention can be applied will be described with reference to an image forming apparatus having contact charging means and contact transfer means schematically shown in FIG. The developing method of the present invention can also be applied to an image forming method using a corona charging method and / or a corona transfer method.

Photoconductive layer 801a and conductive base layer 801b
Is rotated at a predetermined peripheral speed (process speed) in the rotation direction of the clockwise hand on the drawing. A bias is applied to the charging roller 802 having the conductive elastic layer 802a and the core metal 802b by a charging bias power supply 803. The charging roller 802 is
The photosensitive member 801 is pressed against the photosensitive member 801 by pressing force.
It is driven and rotated with the rotation of 01.

When the bias V ₂ is applied to the charging roller 802, the surface of the photoconductor 801 is charged to a predetermined polarity and potential. Next, an electrostatic charge image is formed by the image exposure 804, and is sequentially visualized as a toner image by the developing unit 805.

A bias V ₁ is applied to the developing sleeve constituting the developing means 805 from the developing bias applying means 813. The toner image formed on the latent image holding member by development is transferred to a transfer bias V ₃ by a transfer bias power supply 807.
Is electrostatically transferred to the transfer material 808 by a transfer roller 806 (conductive elastic layer 806a, core metal 806b) as a contact transfer unit that presses the transfer material 808 to which the image has been applied onto the photosensitive member 801. Is heated and pressed by a heating and pressing unit 811 having a heating roller 811a and a pressing roller 811b. Photoconductor 80 after transfer of toner image
On one side, adhered contaminants such as transfer residual toner are cleaned and cleaned by a cleaning device 809 having an elastic cleaning blade pressed against the photoreceptor 801 in the counter direction, and further subjected to static elimination by an exposing and exposing device 810 to repeatedly produce. Imaged.

As described above, the primary charging means has been described using the charging roller 802 as the contact charging means, but may be a contact charging means such as a charging blade or a charging brush, or a non-contact corona charging means. The contact charging means generates less ozone in the charging step.
The transfer unit has been described using the transfer roller 806 as described above, but may be a contact charging unit such as a transfer blade or a transfer belt, or a non-contact corona transfer unit. The contact transfer unit generates less ozone in the transfer process.

Further, another fixing method applicable to the image forming method of the present invention will be described with reference to fixing means shown in FIG. FIG. 5 shows a heating member 511 fixedly supported on a recording material 519 on which a toner-visible image is formed, and a pressurizing member which opposes the heating member and presses the recording material in close contact with the heating member via a film 515. A means for fixing by heating with the member 518 is shown.

In the fixing device shown in FIG.
Has a smaller heat capacity than a conventional heat roll and has a linear heating part, and the maximum temperature of the heating part is 100
It is preferable that it is -300 degreeC.

A fixing film 515 located between the heating element 511 and a pressure roller 518 as a pressure member.
Is preferably a heat-resistant sheet having a thickness of 1 to 100 μm, and these heat-resistant sheets have high heat resistance.
In addition to polymer sheets such as polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, and polyamide, metal sheets such as aluminum, and metal sheets And a laminate sheet composed of a polymer sheet.

A more preferable constitution of the fixing film is that these heat-resistant sheets have a release layer and / or a low-resistance layer.

Reference numeral 511 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus.
The resistive material 513 is applied to an alumina substrate 512 having a length of 0 mm and a length of 240 mm to a width of 1.0 mm. Energization is DC100V cycle 20m
A pulse corresponding to a desired temperature and energy release amount controlled by the temperature detecting element 514 is given by changing the pulse width in a pulse-like waveform of sec. The approximate pulse width is 0.5 msec to 5 msec. The fixing film 515 moves in the direction of the arrow in the figure by contacting the heating element 511 whose energy and temperature are controlled in this manner.

An example of this fixing film has a thickness of 20 μm.
m heat-resistant film (for example, polyimide, polyetherimide, PES, PFA
It is an endless film in which a release layer obtained by adding a conductive agent to a fluororesin such as TFE or PAF) is coated at 10 μm.
Generally, the total thickness is less than 100 μm, more preferably 40 μm.
Less than m is good. The drive of the film is performed by the drive roller 516 and the driven roller 517 and the tension without being wrinkled in the direction of the arrow due to the tension.

Reference numeral 518 denotes a pressure roller having a rubber elastic layer having good releasability such as silicone rubber, and has a total pressure of 39.2.
The heating body is pressurized through the film at １９196 N (4 to 20 kg), and is rotated while being pressed against the film. The unfixed toner 520 on the recording material 519 is guided to a fixing unit by an entrance guide 521, and obtains a fixed image by the above-described heating.

Although the fixing film 515 has been described as an endless belt, a sheet feed shaft and a take-up shaft may be used, and the fixing film may be an edged film.

The methods for measuring the physical properties of the toner of the present invention are listed below.

(1) Measurement of acid value Measurement is performed according to the measurement method described in JIS K0070. Measurement device: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics) Calibration of the device: 120 ml of toluene and 30 ml of ethanol
Is used. Measurement temperature: 25 ° C. Sample preparation: 1.0 g of toner is added to 120 ml of toluene and dissolved by stirring with a magnetic stirrer at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to make a sample solution.

Measurement operation: 1) The sample is used after removing additives other than the binder resin (polymer component) in advance, or the acid value and the content of the components other than the binder resin and the cross-linked binder resin are used. Is obtained in advance. 0.5 to 2.0 (g) of the crushed sample is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when measuring the acid value of the binder resin from the toner, the acid value and the content of the colorant or the magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation. 2) The sample is placed in a 300 (ml) beaker, and 150 (ml) of a mixed solution of toluene / ethanol (4/1) is added and dissolved. 3) Using an ethanol solution of 0.1 mol / l KOH, titrate with a potentiometric titrator (for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win)
workstation) and automatic titration using an ABP-410 motorized burette is available). 4) The amount of the KOH solution used at this time is defined as S (ml), a blank is measured at the same time, and the amount of the KOH solution used at this time is defined as B (ml). 5) Calculate the acid value by the following equation. f is a factor of KOH.

Acid value (mgKOH / g) = ｛(SB) ×
f × 5.61｝ / W

(2) Measurement of molecular weight of THF-soluble component The molecular weight distribution by GPC using THF (tetrahydrofuran) as a solvent for the THF-soluble component of the binder resin or toner was measured under the following conditions. It shall be measured.

Cool the column in a 40 ° C. heat chamber.
And the column at this temperature was treated with TH as solvent.
F at a flow rate of 1 ml / min.
Measure by injecting 0 μl. In measuring the molecular weight of the sample
Shows the molecular weight distribution of the sample by several types of monodisperse polystyrene.
Logarithmic value and count of the calibration curve created by the standard sample
It was calculated from the relationship with the value. Standard polystyrene for creating calibration curves
Examples of the ren sample include Tosoh Corporation and Showa Denko
Molecular weight of 10^Two-10⁷Use something less
It is appropriate to use about 10 standard polystyrene samples.
That's right. In addition, an RI (refractive index) detector is used for the detector.
I have. In addition, use a commercially available polystyrene gel
It is better to combine multiple columns, for example, Showaden
Shodex GPC KF-801, 80
2, 803, 804, 805, 806, 807, 800
P combination or Tosoh TSKgel G10
00H (H_XL), G2000H (H_XL), G3000H
(H_XL), G4000H (H _XL), G5000H
(H_XL), G6000H (H_XL), G7000H
(H_XL), Combination of TSKguard column
Can be mentioned.

By calculating the ratio of the integrated molecular weight of 500,000 or more to the integrated weight of 800 or more from the molecular weight distribution by GPC obtained by the above method, the content of the component having a molecular weight of 500,000 or more can be calculated. Ask.

The sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then TH
The time of leaving in F is set to 24 hours or more. After that, sample processing filter (pore size 0.2 ~
0.5 μm, for example, Mysholi Disc H-25-2
(Manufactured by Tosoh Corporation) can be used. ) Is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

(3) Measurement of THF Insoluble Content 0.5 to 1.0 g of a toner sample was weighed (W ₁ g),
A cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kabushiki Kaisha) is put into a Soxhlet extractor, and THF 200m is used as a solvent.
After extracting with a solvent for 10 hours, evaporating the soluble component solution extracted with the solvent, vacuum drying at 100 ° C. for several hours, and weighing the amount of the THF soluble resin component (W
₂ g). Find the weight other than the resin component in the toner (W
₃ g). The THF-insoluble content is obtained from the following equation.

[0161]

(Equation 1)

Alternatively, the extract component (W ₄ g) is weighed,
The THF-insoluble matter may be determined from the following equation.

[0163]

(Equation 2)

(4) Measurement of Endothermic Peak Temperature of Wax ASTM D3418-8 was measured using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained. The temperature of the endothermic main peak is defined as the melting point of the wax.

(5) Measurement of DSC Curve of Toner A DSC curve in the process of raising the temperature of the toner is measured in the same manner as in the measurement of the melting point of the wax.

(6) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C. In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(7) Measurement of molecular weight distribution of wax GPC measuring device: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol) Addition) Flow rate: 1.0 ml / min Sample: Inject 0.4 ml of 0.15% sample Under the above conditions, the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. Further, it is calculated by converting to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

(8) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by mass. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 80
6,807 combinations are preferred.

(9) Measurement of Particle Size Distribution of Toner The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method,
To 100 to 150 ml of the electrolytic aqueous solution, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is approximately 1 to
The dispersion treatment was performed for 3 minutes, and the measurement apparatus used a 100 μm aperture as a 2 μm aperture.
The volume and number of the toner were measured to calculate the volume distribution and the number distribution.

(10) Measurement of dielectric loss tangent of toner Using a 4284A Precision LCR meter (manufactured by Hewlett-Packard Company), calibration was performed at frequencies of 1 kHz and 1 MHz. = Ε ″ / ε ′).

0.5 to 0.7 g of the toner was weighed, and 392
A load of 00 kPa (400 Kgf / cm ² ) is molded for 2 minutes to obtain a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm).
This measurement sample is put into a 25 mm diameter dielectric constant measuring jig (electrode).
Is attached to ARES (manufactured by Rheometric Scientific F.E.), and heated to a temperature of 150 ° C. and fixed by melting. Thereafter, the sample is cooled to a temperature of 25 ° C., and is obtained by measuring in a frequency range of 100 Hz to 1 MHz including 100 kHz under a load of 500 g.

(11) Measurement of ¹³ C-NMR (nuclear magnetic resonance) spectrum Measurement apparatus: FT NMR apparatus JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 100.40 MHz Pulse condition: 5.0 μs Data point: 32768 Frequency range: 10500 Hz Integration frequency: 20000 times Measurement temperature: 40 ° C. Sample: 200 mg of the measurement sample is placed in a φ10 mm sample tube, and the solvent as a CDCl ₃ was added, which was dissolved in a thermostat at 40 ° C. is prepared.

[0181]

The present invention will be described below with reference to production examples and examples.

Production of Hybrid Resin: [Production Example 1]-24 mol% of terephthalic acid-21.5 mol% of isophthalic acid-2.5 mol% of fumaric acid-bisphenol A derivative represented by the formula (2) (R: ethylene group , X + y = 2.2) 52 mol% An esterification catalyst is added to the carboxylic acid and alcohol to undergo condensation polymerization to substantially contain no THF-insoluble components.
An unsaturated polyester resin (U-1) constituting a polyester unit of a hybrid resin component having an acid value of 17 mgKOH / g, a glass transition temperature (Tg) of 61 ° C, and a peak molecular weight of 9,500 was obtained.

Next, 200 parts by mass of xylene was added to the reflux tube,
After charging into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dropping device, and a decompression device, 100 parts by mass of the unsaturated polyester (U-1) is added, and nitrogen is introduced into the reaction vessel. The temperature was heated to 115-120C. Next, a monomer mixture consisting of 82 parts by mass of styrene forming a vinyl polymer unit, 16 parts by mass of butyl acrylate, and 1 part by mass of di-t-butyl peroxide as a polymerization initiator was added, and radical polymerization was carried out for 8 hours. The reaction was performed. When the molecular weight and the acid value of the hybrid resin composition obtained by removing xylene were measured, the molecular weight was 8,000.
And a glass transition temperature (Tg) of 6
At 2.3 ° C., the acid value was 22 mgKOH / g, and it had a THF-insoluble content of about 26% by mass. This is designated as hybrid resin composition (H-1) of the present invention.

[Production Example 2] A main peak having a molecular weight of 11500 was obtained in the same manner as in Production Example 1, except that a monomer mixture comprising 86 parts by mass of styrene and 14 parts by mass of butyl acrylate was used as the vinyl polymer unit. The glass transition temperature (Tg) was 64.7 ° C., and the acid value was 21.
A hybrid resin composition (H-2) having a concentration of mgKOH / g and a THF-insoluble content of about 20% by mass was obtained.

[Production Example 3] The same procedure as in Production Example 1 was carried out except that a monomer mixture comprising 74 parts by mass of styrene, 24 parts by mass of butyl acrylate, and 2 parts by mass of acrylic acid was used as the vinyl polymer unit. 10,000
It has a main peak at 0 and a glass transition temperature (Tg) of 6
At 4.7 ° C., the acid value was 28 mg KOH / g, and a hybrid resin composition (H-3) having a THF-insoluble content of about 41% by mass was obtained.

[Production Example 4] The wax was prepared in the same manner as in Production Example 1 except that the wax (2) shown in Table 3 was added to 5 parts by mass of xylene to produce a vinyl polymer unit. Containing hybrid resin composition (H-
4) was obtained.

[Production Example 5] A wax-containing hybrid resin was produced in the same manner as in Production Example 1 except that a vinyl polymer unit was produced by adding 5 parts by mass of wax (3) to xylene. A composition (H-5) was obtained.

Production Example 6 A wax-containing hybrid resin was produced in the same manner as in Production Example 1 except that a vinyl polymer unit was produced by adding 5 parts by mass of wax (5) to xylene. A composition (H-6) was obtained.

[Production Example 7] A vinyl polymer unit was produced in the same manner as in Production Example 1 except that 2.5 parts by mass of wax (3) and 2.5 parts by mass of wax (5) were added to xylene. A hybrid resin composition (H-7) containing wax was obtained in the same manner as in Example 1.

[Production Example 8]-42 mol% of terephthalic acid-3 mol% of isophthalic acid-1.5 mol% of fumaric acid-bisphenol A derivative represented by the formula (2) (R: ethylene group, x + y = 2.2) 53.5 mol% The above carboxylic acid and alcohol are added with an esterification catalyst and subjected to polycondensation to substantially contain no THF-insoluble components.
Acid value is 6 mgKOH / g, glass transition temperature (Tg) is 6
An unsaturated polyester resin (U-2) constituting a polyester unit of the hybrid resin composition having a peak at 1 ° C. and a molecular weight of 6,500 was obtained.

65 parts by mass of styrene, 27 parts by mass of butyl acrylate, 8 parts by mass of monobutyl maleate, 0.3 part by mass of divinylbenzene, and 0.1 part by mass of benzoyl peroxide 0.1 part by mass as the polymerization initiator.
Dissolved in a monomer mixture consisting of 5 parts by mass and charged into a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube containing 2 parts by mass of polyvinyl alcohol and 200 parts by mass of degassed ion-exchanged water. And suspend. The mixture was heated to 77 ° C. while passing nitrogen, kept at that temperature for 20 hours, further heated to 95 ° C., and kept at that temperature for 2 hours to complete the polymerization reaction. The suspension after completion of the reaction was separated by filtration, washed with water and dried to give Tg = 56.5 ° C. and an acid value of about 16 mg.
A hybrid resin composition (H-8) having a KOH / g content of about 36% by mass of a THF-insoluble matter was obtained.

[Production Example 9] A hybrid containing a wax in the same manner as in Production Example 7 except that 100 parts by mass of the unsaturated polyester resin (U-3) and 5 parts by mass of the wax (2) were added. Resin composition (H-
9) was obtained.

[Production Example 10] A hybrid containing a wax in the same manner as in Production Example 7 except that 100 parts by mass of the unsaturated polyester resin (U-3) and 5 parts by mass of the wax (3) were added. Resin composition (H-
10) was obtained.

[Production Example 11] A hybrid containing a wax in the same manner as in Production Example 7 except that 100 parts by mass of the unsaturated polyester resin (U-3) and 5 parts by mass of the wax (5) were added. Resin composition (H-
11) was obtained.

[Production Example 12] In Production Example 7, except that 2.5 parts by mass of the wax (3) and 2.5 parts by mass of the wax (5) were added together with 100 parts by mass of the unsaturated polyester resin (U-3). A hybrid resin composition (H-12) containing wax was obtained in the same manner as in Production Example 7.

[Comparative Production Example 1] ・ 24 mol% of terephthalic acid ・ 22 mol% of isophthalic acid ・ 54 mol% of 1,4-cyclohexanediol 80 parts by mass of styrene and acrylic acid using a polyester resin comprising the above carboxylic acid and alcohol Butyl 16
A main peak having a molecular weight of 1700 in the same manner as in Production Example 1 except that a monomer mixture comprising 10 parts by mass of di-t-butyl peroxide as a polymerization initiator was used. , Acid value is 45
A comparative hybrid resin (R-1) having a concentration of mgKOH / g and a THF-insoluble content of about 0.5% by mass was obtained.

[Comparative Production Example 2]-24 mol% of terephthalic acid-22 mol% of isophthalic acid-2 mol% of fumaric acid-52 mol% of 1,4-cyclohexanediol 52 mol% of a polyester resin comprising the above carboxylic acid and alcohol, and styrene 65 parts by mass, butyl acrylate 3
A main peak was reached at a molecular weight of 18,000 in the same manner as in Production Example 1 except that a monomer mixture consisting of 4.5 parts by mass, 0.5 parts by mass of divinylbenzene, and 0.2 parts by mass of benzoyl peroxide was used as a polymerization initiator. Having an acid value of about 0.5 mg KOH / g and 55% by weight of THF
A comparative hybrid resin (R-2) having an insoluble content was obtained.

Production of monoazo iron compound: [Production Example 13] 0.05 mol of exemplified monoazo compound (2)
1 is 500 m of N, N-dimethylformamide (DMF)
and stirred. Sodium carbonate 0.03m
was added and the temperature was raised to 70 ° C., and 8.3 g of ferrous sulfate heptahydrate was added, followed by a reaction for 5 hours. This reaction solution was dispersed in water, and the obtained precipitate was collected by filtration, washed with water, and dried to obtain a monoazo iron compound (I).

[Production Example 14] A monoazo iron compound (II) was obtained in the same manner as in Production Example 13, except that the exemplified monoazo compound (1) was used instead of the exemplified monoazo compound (2).

Example 1 105 parts by mass of hybrid resin (H-4) 90 parts by mass of magnetic material (average particle size 0.22 μm, coercive force 9.6 kA / m, saturation magnetization 83 Am ² / kg, residual magnetization) 15 Am ² / kg) 2 parts by mass of monoazo iron compound (I) The above raw material mixture was melt-kneaded by a twin-screw kneading extruder heated to 130 ° C. The kneaded product was allowed to cool, coarsely pulverized by a cutter mill, and then finely pulverized by a jet mill, and the obtained finely pulverized product was classified by an air classifier to obtain a weight average particle size of 7.4.
A μm magnetic toner (1) was obtained.

When the THF insoluble content of this toner was measured, it was found to be 26% by mass based on 100 parts by mass of the binder resin. When the molecular weight of the THF-soluble component was measured, the peak molecular weight was 8000, the component having a molecular weight of 100,000 to less than 10,000,000 was contained at 11% by mass, and the molecular weight was 5,000 to 1,
It contains 64% by mass of a component having a molecular weight of less than 100,000
It contained 25% by mass of components from 0 to less than 5000. When the acid value of the toner was measured, it was found to be 11 mgK
OH / g. When a ¹³ C-NMR spectrum of a sample in which the magnetic substance was dissolved and removed from the toner with hydrochloric acid was measured, a new signal was detected at about 168 ppm.
It was confirmed that the hybrid resin component was present.

To 100 parts by mass of the magnetic toner, 1.0 part by mass of hydrophobic dry silica (BET specific surface area: 200 m ^{2 /} g) was externally added using a Henschel mixer to obtain a toner.

Using this toner, a copying machine G manufactured by Canon
Evaluation of image characteristics and evaluation of toner adhesion to the fixing member were performed using P-215 (process speed: 105 mm / sec, surf fixing) and Canon copier NP-6085 (process speed: 513 mm / sec, hot roll fixing). Good results as shown in Table 5 were obtained.

Next, the fixing unit of the NP-6085 was removed, and a fixing test device equipped with an external driving device, a temperature control device for the fixing device, and a device for adjusting the pressing force of the roller was prototyped. Roller peripheral speed 150mm / sec, total pressure 392
Using an unfixed image developed with a toner that gives an image density of 1.2 as N (40 Kgf), a low-temperature fixing test was performed by setting the roller surface temperature to 150 ° C., and the roller surface temperature was set to 220 ° C. When the hot offset resistance was evaluated by using this method, good results as shown in Table 5 were obtained.

<Examples 2 to 16> Magnetic toners (2) to (15) of the present invention were produced and evaluated in the same manner as in Example 1 except that the hybrid resins and waxes shown in Table 4 were used.

All the hybrid resins are ¹³ C-
NMR measurement confirmed that the resin contained a hybrid resin component.

Comparative Example 1 Comparative hybrid resin (R-1) 100 parts by mass Magnetic substance 90 parts by mass (average particle size 0.22 μm, coercive force 9.6 kA / m, saturation magnetization 83 Am ² / kg, Residual magnetization 15 Am ² / kg)-2.5 parts by mass of comparative wax (1)-1.5 parts by mass of monoazochrome compound for comparison (compound consisting of 2 mol of the following monoazo compound (1) for comparison and 1 mol of chromium atom) A comparative magnetic toner (1) was produced in the same manner except that the comparative hybrid resin, wax and the like were used. Table 5 shows the evaluation results.

Comparative Example 2 A comparative magnetic toner (2) was produced in the same manner as in Comparative Example 1, except that 5 parts by mass of the comparative wax (2) was used. Table 5 shows the evaluation results.

Comparative Example 3 A comparative magnetic toner (3) was produced in the same manner as in Comparative Example 1, except that the comparative hybrid resin (R-2) was used as the binder resin. Table 5 shows the evaluation results.

Comparative Example 4 A comparative magnetic toner (4) was produced in the same manner as in Comparative Example 3, except that 5 parts by mass of the comparative wax (2) was used. Table 5 shows the evaluation results.

Comparative Example 5 In Comparative Example 1, a monoazo iron compound for comparison (the following monoazo compound (2) 2 for comparison)
Comparative Magnetic Toner (5) was produced in the same manner except that a compound consisting of 1 mol of iron and 1 mol of iron atom) was used. Table 5 shows the evaluation results.

[0212]

Embedded image

Rank of low-temperature fixability Rank 5: Density reduction rate by rubbing is less than 5% Rank 4: Density reduction rate by rubbing is less than 10% Rank 3: Density reduction rate by rubbing is less than 15% Rank 2 : Density reduction rate due to rubbing is less than 20% Rank 1: Density reduction rate due to rubbing is 20% or more

Rank of hot offset Rank 5: No occurrence at all Rank 4: Minor offset occurrence, but practically acceptable Rank 3: Offset occurrence that can be easily discriminated visually Rank 2: Notable offset occurrence Rank 1: Paper wraps around rollers

Evaluation of toner blocking (evaluated by leaving it in an environment of 50 ° C. for 72 hours) Rank 5: No change in toner fluidity Rank 4: Toner fluidity is slightly reduced Rank 3: Aggregate of toner is seen, but loosened easily (practically acceptable) Rank 2: Aggregate of toner is seen, with core and not completely loose Rank 1: Caking

[0216]

[Table 3]

[0217]

[Table 4]

[0218]

[Table 5]

[0219]

According to the present invention, in addition to the sufficient low-temperature fixability and high-temperature offset resistance of the toner, good developability can be exhibited in each environment of high temperature, high humidity, and normal temperature and normal humidity.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a developer supply system developing device in which a developer carrier is incorporated (a magnetic blade is used as a regulating member).

FIG. 2 is a schematic diagram illustrating an example of a developer supply-type developing device in which a developer carrier is incorporated (an elastic blade is used as a regulating member).

FIG. 3 is a schematic view of a cross section of a part of a developer carrier.

FIG. 4 is a schematic explanatory view of an image forming method.

FIG. 5 is a schematic diagram of a fixing device applicable to the image forming method.

Claims (39)

[Claims] 1. A toner containing a binder resin, a colorant, a wax and an organic iron compound, wherein (a) the acid value of the binder resin of the toner is 2 to 40 mg KOH / g, and (b)
The binder resin of the toner contains a hybrid resin component having a polyester unit and a vinyl polymer unit, and (c) the binder resin of the toner has 2 to 50% by mass of tetrahydrofuran (based on the binder resin). TH
F) a tetrahydrone (THF) -soluble component in the binder resin of the toner (d) having a main peak at a molecular weight of 2,000 to 15,000 in a chromatogram measured by gel permeation chromatography (GPC). 5 to 40% by mass of a component having a molecular weight of 100,000 to less than 10,000,000, and a molecular weight of 5,000 to 10
It contains 40 to 70% of less than 10,000 components and has a molecular weight of 10
10 to 30% by mass of a component of from 00 to less than 5000
And (e) an organic iron compound represented by the following formulas (I) to (I)
A toner comprising a complex and / or a complex salt comprising the monoazo compound represented by I) and an iron atom. Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R
₈ is each independently hydrogen, halogen, nitro,
A linear or branched alkyl or haloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group,
It represents a substituent selected from the group consisting of a substituted or unsubstituted aralkyl group. ) (Wherein, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ ,
R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ each independently represent hydrogen, a halogen, a nitro group, a linear or branched alkyl or haloalkyl group having 1 to 20 carbon atoms,
It represents a substituent selected from the group consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted aralkyl group. ) 2. The toner according to claim 1, wherein the binder resin has an acid value of 5 to 30.
The toner according to claim 1, wherein the amount is mgKOH / g. 3. The toner according to claim 1, wherein the binder resin has an acid value of 7 to 25.
The toner according to claim 1, wherein the amount is mgKOH / g. 4. The binder resin of the toner has a THF insoluble content of 5%.
The toner according to any one of claims 1 to 3, wherein the content of the toner is from 1 to 40% by mass. 5. The toner according to claim 1, wherein the binder resin of the toner has a THF-insoluble content of 7%.
The toner according to any one of claims 1 to 3, wherein the content of the toner is from 30 to 30% by mass. 6. The toner according to claim 1, wherein the THF-soluble component of the binder resin of the toner has a main peak in a region having a molecular weight of 3,000 to 10,000. 7. The toner according to claim 1, wherein the THF-soluble component of the binder resin of the toner has a main peak in a region having a molecular weight of 4,000 to 9000. 8. The toner according to claim 7, wherein said binder resin has a THF-soluble component having a molecular weight of 100,000 or more and less than 10,000,000.
The toner according to any one of claims 1 to 7, which is contained by mass%. 9. A toner having a THF-soluble component in a binder resin of the toner having a molecular weight of 100,000 or more and less than 10,000,000 is contained in an amount of 10-3.
The toner according to any one of claims 1 to 7, wherein the toner is contained in an amount of 0% by mass. 10. A toner having a THF-soluble component in a binder resin of the toner having a molecular weight of 5,000 to less than 100,000 to 42 to 6
The toner according to any one of claims 1 to 9, wherein the toner content is 8% by mass. 11. A toner having a THF-soluble component having a molecular weight of 5,000 or more to less than 100,000 in a binder resin of the toner, comprising 45 to 6
The toner according to any one of claims 1 to 9, wherein the toner content is 5% by mass. 12. The toner according to claim 1, wherein a THF-soluble component of the binder resin of the toner contains 12 to 28% by mass of a component having a molecular weight of 1,000 to less than 5,000.
The toner according to any one of the above. 13. The toner according to claim 1, wherein a THF-soluble component of the binder resin of the toner contains 15 to 25% by mass of a component having a molecular weight of 1,000 to less than 5,000.
The toner according to any one of the above. 14. The toner according to claim 1, wherein the toner contains 0.1 to 5% by mass of an organic iron compound. 15. The toner according to claim 1, wherein the toner contains an organic iron compound in an amount of 0.5 to 3% by mass. 16. The toner according to claim 1, wherein the toner contains an organic iron compound in an amount of 0.7 to 2% by mass. 17. The organic iron compound contained in the toner can form a THF (tetrahydrofuran) insoluble component by interacting with a carboxyl group contained in a polyester as a binder resin. 17. The toner according to any one of 1 to 16. 18. The toner according to claim 1, wherein an organic iron compound contained in the toner is added as a charge control agent. 19. The wax having a molecular weight of 400 to 2,000.
19. The toner according to claim 1, having a main peak at 0 and a ratio (Mw / Mn) of 1.2 to 20. 20. The wax having a molecular weight of 700 to 1500.
19. The toner according to claim 1, having a main peak at 0 and a ratio (Mw / Mn) of 1.5 to 15. 21. The wax having a molecular weight of 900 to 1000.
19. The toner according to claim 1, having a main peak at 0 and a ratio (Mw / Mn) of 1.7 to 10. 22. The toner according to claim 1, wherein the wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer. 23. The toner according to claim 1, wherein the wax has a structure represented by the formula (1). Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 24. A wax having a concentration of 1 to 20 mg KOH / g.
The toner according to any one of claims 1 to 21, wherein the toner is an acid-modified polypropylene having the following acid value: 25. A wax comprising 1 to 20 mg KOH / g
The toner according to any one of claims 1 to 21, wherein the toner is an acid-modified polyethylene having an acid value of: 26. The method according to claim 26, wherein the wax is a differential scanning calorimeter (DS).
The toner according to any one of claims 1 to 25, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured in C) is 70 to 150 ° C. 27. The method according to claim 27, wherein the wax is a differential scanning calorimeter (DS).
The toner according to any one of claims 1 to 25, wherein the melting point defined by the endothermic peak temperature at the time of temperature rise measured in C) is 75 to 140 ° C. 28. The method according to claim 28, wherein the wax is a differential scanning calorimeter (DS).
The toner according to any one of claims 1 to 25, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured in C) is 85 to 130 ° C. 29. It contains two different waxes, has a main peak at a molecular weight of 300 to 20,000, and has a ratio (M
2. The toner according to claim 1, wherein (w / Mn) is from 1.5 to 25. 30. It contains two different waxes, has a main peak at a molecular weight of 400 to 15,000, and has a ratio (M
2. The toner according to claim 1, wherein (w / Mn) is 1.8 to 22. 31. It contains two different waxes, has a main peak at a molecular weight of 500 to 10,000, and has a ratio (M
The toner according to claim 1, wherein (w / Mn) is 2 to 20. 32. The method according to claim 1, wherein the at least one wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer.
Or the toner according to any one of 29 to 31. 33. The at least one wax of formula (1)
3. A structure having a structure represented by:
32. The toner according to any one of 9 to 31. Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 34. The composition according to claim 34, wherein the at least one wax is from 1 to 2
32. The toner according to claim 1, which is an acid-modified polypropylene having an acid value of 0 mgKOH / g. 35. The method according to claim 35, wherein the at least one wax is 1 to 2
The toner according to any one of claims 1 to 29, wherein the toner is an acid-modified polyethylene having an acid value of 0 mgKOH / g. 36. The toner according to claim 1, wherein at least one type of wax is added during the production of the binder resin. 37. The toner has a dielectric loss tangent (tan δ) measured at a frequency of 100 kHz of 3 × 10 ^{−3 to} 3 × 10 ^−2.
The toner according to any one of claims 1 to 36, wherein: 38. The toner has a dielectric loss tangent (tan δ) measured at a frequency of 100 kHz of 4 × 10 ^{−3 to} 2 × 10 ^−2.
The toner according to any one of claims 1 to 36, wherein: 39. The toner has a dielectric loss tangent (tan δ) measured at a frequency of 100 kHz of 5 × 10 ^{−3 to} 1.5 × 1.
The toner according to any one of claims 1 to 36 characterized in that it is a 0 ^-2.